Dialkyl acyloxyalkylphosphonates



2,929,831 lCfi Patented Mar-.22, 1960 United States Patent In the following enample's, commercial triethyl phosphite, tributyl phosphite, and trihexyl phosphite were employed.- These were freshly distilled before use.

EXAMPLE 1 Diethyl lauroxyezhylphosphonate Fifty-two grams (0.17 mole) of 2-bromoethyl laurate was mixed with 58 grams (0.35 mole) of triethyl phos- 2,929,ss1 DIALKYL ACYLOXYALKYLPHOSPHONATES Bernard Ackerman, Elkins Park, and Daniel Swern, Philadelphia, Pa., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application OctobcrlO, 1956 Serial No. 615,206

5 Claims. (0 260-461) (Grantedunder 'l'itle 5, U.S. Code (1952), sec.-266) index became constant.: The-reaction mixture was vacuum distilled, yielding 35 .grams of diethyl lauroxyethyl phosphonate having a..boiling point of 162464 C. 'at' 0.2mm.andan 1.4419. s v v, H Analysis.-y-.Calculated ."for .CmHg 0 Pz. P='8i50%.

A non-exclusive, irrevocable, royalty-free license in the 1d Found: invention hereindescribed, throughout the world for r all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby malkyl phosphltes' ranted to the Government of the United States of In Table P are listed the bromoalkyl America esters used and their properties:

This invention relates to a new class of organic phos above, other bromoalkyl esters were reacted with other TABLE I phorus-containing compounds. More particularly, it relates to a new class of dialkyl acyloxyalkylphosphonates -g, C. "0 having the general formula, 5

2 E 2-1 3r imoethyl lllalrage (Used 114-9/0.6 mm 1.4564. 1 mxampes,,. R 0 f" 2-Bromoethyl Myristate 15760/0.91nm- 1.4539.

OR (I) 2 h ;t h i 1 i t t 43 1 4507 (5 *0 1'0 0 9. ml 8. G 0 In the above formula, R is either an ethyl, butyl, or (Used in Ex ample a o hexyl radical; R is an aliphatic hydrocarbon radical, 3o g gflggggg 49 1-4500 (55 preferably having from 11-17 carbon atoms and may 2-] 3roEmoeth317l5)Oleate (Used 185-6/O.6mm.... 1.4669.

'1 1n xampe be either saturated or unsaturated, and n 1s 2 01 J. 3 Brom0propy1Laumtc(Used HIM M585 As snown m Table II, below, compounds fallmg within Example 8). in this class in which R has from 11 to 17 carbon atoms phite and the solution was refluxed '-until the refractive" In a manner similar to that described in Example 1,

have been found to be excellent low temperature plas- In Table II, below, there are listed, in addition to the compound produced according to the detailed procedure of Example 1, compounds produced, following the In general, according to this invention, the compounds method of Example 1, in which the bromoalkyl esters are produced by esterifying a fatty acid with a bromolisted in Table I were reacted with other trialkyl alkyl alcohol and then reacting the resulting bromophosphites:

TABLE II II R DIALKYL AOYLOXYALKYLPHOSPHONATES: R0-O-(CH:) r-P -+0 Phosphorus, Example Per- B.P., 0.] Percent N 0. can 1; mm. Hg d4 N Yield Calcd. Found R'= 011E214; R= CzH5; 'n=2 57 1. 4419 8. 5 8. 6 R'= Cn n; R CaHs; n=2 66 1. 4440 7. 9 8. 0 R=O 5Haz; R=C2Hs;'!1=2 1.4452 7.4 7.4 R= CuHas; R= CzHa; 'n=2 64 1. 14%) 6. 9 7. 3

5 R'=Ci7H3a; R=C2H5H1=2 53 1. 4542 6. 9 6. 6 R'=C11H23; R=C4HM 7l=2 1.4440 7.4 7.9 1l 2t; =CaH1a; n=2 59 1. 4459 6. 5 7.3 8 R= 011 23; R= (LE9; 7L=3 47 1. 4451 7.1 7. 4

alkyl ester with a trialkyl phosphite to produce the desired In order to evaluate the utility as plasticizers of comdialkyl acyloxyalkylphosphonate. pounds produced according to this invention, several The above-described process may be represented by 6 were combined with a synthetic resin according to the the following equations: following recipe:

A id (0) RL-OH+HO(CH2)nBrfi; R -O(CH Br Parts a US (Bromoalkyl ester) 11 65 Vinyl chloride-vinyl acetate copolymer (:5) 64 OR 0 0R Plasticizer 34 I Heat 1; i, Stabilizers 2 (b) Milled and then molded at 300 F.

R R (D (trlalkyl phosphlte) (dialkylacyloxyalkyl-phosphonate) 70 For purposes of comparison, a commercial plasticizer,

In the above equations, R, R and n have the same dioctyl phthalate, was also used. The results of these significance as above.

tests are summarized in Table III, below:

TABLE 111 EVALUATION OF SOME DIALKYL ACYLOXYALKYL- PHOSPHONATES AS PLASTICIZERS [For Vinyl Chlorldez Acetate Gopolymelz] Tliis il Elonga 100% Clash- Compimnd Tested Strength, tion, Modulus, Berg,

' I p.s.i. Percent p.s.i. 0

Example 6, Table 11 2, e40 380 1,200 --52 Example 7, Table II 2, 720 370 1, 420 -53 Example 8, Table II 2,600 340 1,390 -47.5 Dioetyt Phthalate (Commet-012.1) 3,030 390 1, s00 -25 As can readily be seen the products of this invention compare favorably with dioctyl phthal'ate when used to plasticize'a 95:5 vinyl chloride: vinyl acetate copol'ym'er.

We claim: I 1. A dialkyl acyloxyalkylphosphonate having the formula n -il-e-zem-p-ee where R is a radical selected from the map consisting of ethyl; butyl, and hexyl, R is an aliphatic hydrocarbon radical having from 11-17 carbon atoms, anti n is an integer from the group consisting of 2 and 3.

2. Diethyl lauroxyethylphosphonate. 3. Dibutyl lauroxyethylphosphonate. 4. Dihexyl lauroxyethyl'phosphonate. 5. Dibutyl latiioxyjir'opylphos'phonat.

10 References Cited in the file of this patent UNITED STATES PATENTS 2,668,800 Johnston s.t;. Feb. 9, 1954 2,710,301 Morris et al. un-ecu". Jan. 7, 1955 15 L i. FOREIGN PATENTS 694,772 Great Britain Tu'ly 2'9, 1953 509,034 (Danada Jan. 11, 1955 2D OTHER Puaevim chem. Abstract, vol. #7, col. 268-8 (1953). 

1. A DIALKYL ACYLOXYALKYLPHOSPHONATE HAVING THE FORMULA 